KR20050085802A - Epoxy-functional hybrid copolymers - Google Patents

Abstract

Versatile synthetic methodology has been established for the production of a variety of siloxane and silane-containing radial epoxy resins and intermediates. This chemical approach has been exploited to obtain a variety of hybrid organic/inorganic materials that can be described as epoxysiloxane or epoxysilane radial copolymers. The methodology can be used to access reactive, hydrophobic Si-containing resins with good organic compatibility that are structurally distinct from epoxy-functional siloxanes/silanes known in the prior art. These hybrid radial epoxy resins may be utilized for a variety of adhesive and coating applications including radiation and thermally curable sealants, encapsulants and adhesives.

Description

Epoxy Functional Hybrid Copolymer {EPOXY-FUNCTIONAL HYBRID COPOLYMERS}

The present invention relates to reactive organic / inorganic hybrid molecules and copolymers.

UV curable and heat curable materials having epoxy functionality are widely used in the field of adhesives, coatings, films and composite materials. Advantages of using such epoxy-based materials include good adhesion, various curing mechanisms and curing rates, inexpensive and easy to obtain raw materials, and good chemical resistance. As materials used in the above-mentioned fields, chemicals such as cyanate esters and maleimide resins have recently been developed, but they are epoxy resins because they do not vary in kind and fall short of the wide range of applications and lifetimes of epoxy technology. The usefulness of the material is drawing attention. While such epoxy materials are used throughout the industry, there are some shortcomings for use in industrial applications using thermally curable and UV curable materials. Conventional epoxy resin described below is a relatively high degree of curing, is cured in a high T _g material. However, in general, the upper limit of the temperature using the epoxy-based material is in the range of 150 ° C to 180 ° C, which is somewhat lower than the temperature required for various applications. In addition, most epoxy materials have levels of up to several percent by weight in high humidity conditions. Since most epoxy materials exhibit this level of water absorption, epoxy materials are not desirable for various applications, especially in the field of adhesives and coatings for electronic components.

The most common epoxy resins are aromatic molecules such as bisphenol A diglycidyl ether (DGEBPA), or epoxidized novolak resins (such as those from EPON ^® series available from Shell Chemical). These resins derived from the reaction of epichlorohydrin with alcohol (or the same amount of synthesis process) are most often used for thermal curing applications. On the other hand, as the UV curable system (cyclic curable system) epoxy system of the cyclic aliphatic type (e.g. ERL 4221 or ERL 6128 commercially available from Union Carbide) is the most widely used because it shows a fast cation curing reaction rate. Typically, rubberized epoxy derived from the chain extension reaction between rubber having amino or carboxy termini and bis (epoxide) is an epoxy functional material that forms a film. However, all of the aforementioned systems have at least one of the drawbacks of the aforementioned epoxy-based systems. In particular, those that are commercially available as cured cyclic aliphatic epoxy materials have a problem of high rigidity.

Accordingly, in order to improve the flexibility, thermal stability, and water resistance of conventional epoxy materials, a method of incorporating siloxane resins into the cured epoxy matrix has been proposed. Various “epoxysiloxanes”, for example, by chain extension reactions between siloxanes having carbinol ends and bis (epoxides), and by hydrosilation of unsaturated epoxides in SiH functional siloxane materials. Several methods have been proposed including terminal reactions. However, since the SiH functional group, the epoxide functional group, and the remaining transition metal catalyst (particularly, platinum) exist in the synthesis reaction by the hydrosilylation reaction, there is a problem that a variable unstable product is obtained. As a method for this, a method of completely consuming SiH functional groups as much as possible in carrying out the above-described synthesis reaction has been proposed. In this regard, attention has been paid to those skilled in the art on how to fully consume the silicon-hydride functional groups on the various silicon backbones.

And as a method of suppressing the polymerization reaction of the epoxide which arises in presence of SiH group in the hydrosilylation reaction mentioned above, it is known to use a rhodium type catalyst. On the other hand, techniques including monohydrosilation of disilanes and disiloxanes of this class have been used to obtain SiH functionalized molecules and intermediate products. According to some documents, it is described that materials with both SiH and epoxy functional groups can be synthesized. However, using the limited intermediate products described in these documents, no products with high molecular weight controlled structures and / or epoxy-based inclusions are produced. It is also known to cap the ends of linear copolymers of poly (dimethylsiloxane) with silicone hydride ends and bifunctional polyethers (typically poly (propylene glycol) with allyl ends) with epoxy. have. The linear copolymer obtained in this way has improved compatibility with organic materials. However, the number of functional groups of the linear copolymer is limited to two (up to two epoxy groups per linear polymer), and except for those derived from poly (ether), silane inorganic repeating units, or organic dienes are compounded to extend the ends. You can't. Therefore, it is not appropriate to use the aforementioned polymers in applications where high levels of cure density are to be obtained. The molecular structure of such linear copolymers is not clearly defined, and the materials described above exhibit typical molecular weight distributions in conventional “one stage” polymerization reactions. Materials and viscoelastic properties affected by molecular weight distribution are known.

In addition, methods and uses for the synthesis of diene-siloxane copolymers (precursors of such epoxy functional materials) having SiH or olefin ends are known in the literature, but the synthesis methods are suitable for synthesizing radial structures as described herein. It's not an advanced way to do it.

Typically, industrially general purpose and useful epoxide resins such as epoxy novolacs, DGEBPA, and representative cyclic aromatic epoxides (eg, ERL-4221, and ERL 6128) are known epoxides and siloxanes known in the art. The miscibility with resin containing all functional groups is poor. It is well known that the "organic miscibility" of the "epoxysilane" known in the prior art is poor. When such epoxysilane is blended with a hydrocarbon resin, macroscopic phase separation occurs rapidly. It is known that the miscibility in some organic materials can be improved by functionalizing the material with alkyleneoxy side chains so that the siloxane material can be applied to a variety of uses (eg, adhesives and coatings for electronic components). The siloxane material obtained by increasing the hydrophilicity becomes a problem.

1 shows the DSC measurement results of a UV cured radial hybrid epoxy (2).

FIG. 2 shows the results of DSC measurements of EPON 828 accelerated and cured by UV. FIG.

3 shows the results of DSC measurements of hybrid epoxy / vinyl ether blends.

4 shows the DSC measurement results of the cured amine-radial hybrid epoxy (5).

FIG. 5 shows the results of DSC measurements of cationically cured radial hybrid epoxy (2). FIG.

Fig. 6 shows the DSC measurement results for the cured product obtained after UV curing the radial hybrid copolymer 9 having a liquid maleimide resin.

Fig. 7 shows the DSC measurement results for the cured product obtained after the thermal hybridization of the radial hybrid copolymer 9 having the liquid maleimide resin.

8 shows the DSC measurement results for the cured product obtained after the cationic thermal curing of the hybrid copolymer 8.

Fig. 9 shows the results of DSC measurement of addition-cured silicon using the radial silane (3).

It is therefore an object of the present invention to provide a process for the synthesis of suitable hydrophobic epoxysilanes with good miscibility, such as hydrocarbon-based epoxy resins. In addition, another object of the present invention is a novel epoxy functional siloxane or silane / hydrocarbon copolymer of linear and “radial” structure, comprising: 1) controllable molecular structure (polydispersity of about 1), 2 A method of synthesizing a copolymer having a suitable silicone, and 3) various levels of epoxy functional groups (generally more than two). In addition, the materials of the present invention 1) improved miscibility with hydrocarbons compared to conventional commercial epoxysilane resins. 2) improved hydrophobicity compared to hydrocarbon-based epoxides, 3) improved thermal stability compared to hydrocarbon-based epoxides, 4) high UV reactivity compared to various commercial epoxides, and 5) conventional cyclic aliphatic epoxides used for UV curing applications. With improved physical properties compared to the side, this is a preferred feature of the invention without the material according to the prior art.

It has also been found that the radial copolymer intermediate product with olefin end and SiH end according to the invention is a novel and useful material. For example, a resin having an alkenyl end can be used as the reactive intermediate product, alone or in combination with other materials. Likewise, a material having an SiH end can be used as the reactive crosslinking agent used in the hydrosilane curing composition.

In preparing various radial epoxy resins comprising siloxanes and silanes, various synthetic methods are known. Among others, studies on chemical methods have been continued to obtain various hybrid organic / inorganic materials, which may be referred to as epoxysiloxanes or epoxysilane radial copolymers. Using this method, a Si-containing resin can be obtained which is structurally separated from the epoxy functional siloxane / silane according to the prior art, and which has good organic miscibility, reactivity, and hydrophobicity.

The hybrid radial epoxy resin can be used for a variety of adhesives and coatings, including radiation and heat curable sealants, encapsulants, and adhesives.

Detailed description of the invention

The most common techniques used to prepare epoxy functional siloxane materials are unsaturated epoxides, various polymeric hydrosiloxanes and small molecule hydrosiloxanes (e.g., poly (methylhydrosiloxane), respectively, and 1,1,3,3). Tetramethyldisiloxane). In addition, this type of process is typically used to bond organic-compatibilizing groups (in addition to hexyl, octyl, or ethyleneoxy groups) to organic silicone resins. This synthesis method can be used to produce many commercially and academically significant materials, but in the absence of very high levels of carbon-based components attached to the siloxanes, organic groups extended from the siloxane "backbone" The basic molecular structure produces materials with limited solubility in organic materials. In addition to lowering the inorganic properties of the siloxanes (eg, alkyleneoxy-modified siloxanes are more hydrophobic) by blending relatively large amounts of organic functional groups, You can try using full functionalization. This also applies to the hydrosilylation reaction of the silane based resin and the unsaturated organic material.

The present invention provides a method for extensively adjusting the organic / inorganic ratio in the development of novel epoxysiloxanes and epoxysilanes. In addition, according to the synthesis method of the present invention, since the units in which siloxane / silane blocks and hydrocarbon blocks are alternately added are repeatedly added, a product having little or no polydispersity can be obtained. In addition, since there are various reaction schemes for synthesizing such a product, physical properties when uncured and cured are preferable, and various organic / inorganic hybrid materials structurally unique can be synthesized. The material thus obtained is a light curable, electron-beam curable, or thermally curable material. The materials are also applied in a variety of applications, including adhesives, sealants, coatings, and coatings or encapsulants for organic light emitting diodes (OLEDs). In particular, the present invention aims to produce hybrid materials having an optimal carbon content in order to improve compatibility with conventional commercially available UV curable and thermally curable reactive materials. Therefore, in preparing blends of the material of the present invention and commercially available carbon-based resins, desirable physical properties are maintained while maintaining the appropriate physical properties (eg, strength, wettability of the substrate, and adhesion) of the organic material as the substrate. Various siloxanes can be obtained. Epoxysiloxanes and epoxysilanes of the present invention can be widely used in a variety of applications, such as conventional carbon-based epoxides, which provide siloxane-type physical properties to a variety of materials.

The basic synthesis process of the present invention includes the step of adding, with control, alternating units of siloxane (or silane) blocks and hydrocarbon blocks to a "core," a central hydrocarbon, typically having more than two functional groups. do. The structure of the radial copolymer obtained through the process may optionally have a SiH terminus or an olefin terminus, and is generally represented by the following structural formulas:

Organic / Inorganic Block Copolymers with Organic Cores and Epoxy Terminations

(In the above structural formula,

 n = 1 to 100, the core is defined as a hydrocarbon unit, block B is an organic unit, block A is a siloxane and / or silane unit, preferably n = 1 to 5, q = 3 to 20, more preferably q = 3 to 6, and when the block B comprises a polyether unit, q must be 3 or more),

Organic / Inorganic Block Copolymers with Organic Cores and SiH Terminations

(In the above structural formula,

 n = 0 to 100, q = 3 to 20, the core is defined as a hydrocarbon unit, block B is an organic unit, block A is a siloxane and / or silane unit, preferably n = 0, q = 3 to 6),

Organic / Inorganic Copolymers Having Olefin Ends

(In the above structural formula,

 n = 1 to 100, q = 3 to 20, preferably n = 1 to 5, and q = 3 to 6).

In addition, in all three structural formulas, R is independently H, linear or branched alkyl, cycloalkyl, aromatic, substituted aromatic, or part of the cyclic ring, and O, S, N, P, Or a hetero atom such as B, but is not limited to the aforementioned hetero atom.

Hereinafter, the most common examples will be described as having the above structure, and those skilled in the art can understand that they are included in the scope of the present invention. In some cases, the core is a hydrocarbon moiety having a plurality of unsaturated substituents. Examples of suitable organic cores include tetraallylbisphenol A; 2,5-diallylphenol, allyl ether; Trimethylolpropane triallyl ether; Pentaerythritol tetraallyl ether; Triallyl isocyanurate; Triallyl cyanurate; Or mixtures thereof. In the above structural formula, when q <3, as the core, diallyl bisphenol A; 1,4-divinyl benzene; 1,3-divinyl benzene, or mixtures thereof may also be used. In some cases, block B is derived from alkyl (eg ethyl), cycloalkyl (eg dicyclopentadienyl), or aromatic (eg dialkylstyryl). Block B comprises one or more linear or branched alkyl units, linear or branched alkyl units containing hetero atoms, cycloalkyl units, cycloalkyl units containing hetero atoms, aromatic units, substituted aromatic units, heteroaromatic units Or a mixture thereof, and examples of the hetero atom include, but are not limited to, oxygen, sulfur, nitrogen, phosphorus, and boron. In addition, the block B is 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,5-hexadiene; Preference is given to those derived from 1,3-butadiene, or a combination thereof. Also, when the olefin end structure is separated, typically the unsaturated end group is derived directly from the unreacted end of the bis (olefin) used as block B. In addition, in some cases, the block A is 1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; Bis (dimethylsilyl) ethane (1,1,4,4-tetramethyldisylethylene); 1,4-bis (dimethylsilyl) benzene; 1,3-bis (dimethylsilyl) benzene; 1,2-bis (dimethylsilyl) benzene, or mixtures thereof. In some cases, the epoxy end groups may be substantially cyclic aromatic or glycidyl, but are not limited to those described above.

Typically, the synthesis process according to the invention comprises a bifunctional olefin (organic block), and a compound comprising two SiHs, such as a siloxane oligomer having a SiH end, or a silane having a SiH end; an “inorganic block”). Together, they can be applied to most unsaturated core molecules. And in most cases, for practical use, excess bis (olefin) compounds and excess bis (silicon hydride) compounds can be removed from the product. The compounds are removed by vacuum evaporation. In general, in order to economically perform the process, the process of collecting and regenerating, while removing such excess reactant by a vacuum distillation process, can be easily performed. However, if the bifunctional repeating unit (diene or bis (SiH) compound) exhibits a chemical property of reacting only at one end under the reaction conditions, the reactant may be used in stoichiometric amounts. And, in the case described above, it is not necessary to remove excess reagents when performing the synthesis process. Thus, in any case, the method according to the invention, even if the activity at the other end of the molecule in the next reaction is lowered by reaction at one end of the bifunctional reactant (at appropriately controlled reaction conditions). Is not affected accordingly. This can usually be seen in the hydrosilylation of TMDS or TMDE with various unsaturated materials. That is, under the appropriate reaction conditions, as already known, one SiH bond may participate in the hydrosilylation reaction, but the second SiH group does not participate in the reaction until a high temperature or more reactive catalyst is used. As another embodiment, bifunctional reactants can be used that include reactors with reactivity that are remarkably distinct from others, in order to obtain reaction selectivity and to avoid using excess repeating unit molecules. Preferred examples thereof include hydrosilylation reactions of dicyclopentadiene (DCPD), and hydrosilylation reactions at norbornenyl double bonds are performed at a higher rate than at cyclopentadienyl double bonds. Although regioselective and chemically selective reactions as described above are known, in some cases, processes using an excess of bis (silicon hydride) compounds and excess bis (olefin) compounds and these compounds obtained through regeneration processes are industrially employed. It is the most efficient chain / arm extension process, and in many cases, it is possible to obtain high purity products. In the use of the multifunctional, radial molecular structure according to the present invention, if the reactant reacts at both ends during the chain extension process using one of the bifunctional reactants, the molecular weight is increased, It should be taken into account that unwanted results such as acidic and gelling reactions can be obtained in a short time.

Extending the organic / inorganic “arm” of the copolymer from the core to the desired “generation”, linearly or radially, to obtain a radial copolymer with SiH terminus, and then the end of the molecule with an unsaturated epoxy molecule. Capping The physical properties of the unsaturated epoxy molecules can vary depending on the end use of the radial copolymer. For example, for use in UV curable applications initiated by cationic polymerization reactions, the ends of the hybrid cyclic aliphatic epoxy resins above the radial copolymer can be capped with vinyl cyclohexene oxide. In addition, allylglycidyl ether is used as the end group precursor as the heat curable material.

And methods for extending the organic / inorganic blocks from siloxanes or other inorganic cores are within the scope of the present invention. This is an effective method that can be usefully used for some applications by increasing the ratio of inorganic to organic in the material. Thus, extended compounds as described above are represented by the following structural formula:

Organic / Inorganic Block Copolymers with Inorganic Cores

In the above case, core ₁ is an inorganic composition, and in some cases, a siloxane having SiH termini. Illustrative cyclic structures as the core ₁ include 1,3,5,7-tetramethylcyclotetrasiloxane (D ′ ₄ ). Examples of other possible Core ₁ compositions include tetrakis (dimethylsiloxy) silane; Octakis (dimethylsiloxy) octaprismosilsequioxane]; And mixtures thereof. In the above structure, block C is an organic diene and block D is an inorganic bis (SiH functional) material. The structures of these blocks and epoxy ends are the same as those shown in the above description of the organic core material, where block B corresponds to block C and block D corresponds to block A in the foregoing description. In addition, as described above, n = 1 to 100, q may be in the range of 1 to 20, but n may be 0 to 100 in a material having an olefin end. If the block C comprises an ether unit, q must be at least 3.

Likewise, structures with inorganic core ₁ may have olefin or SiH terminal functional groups, as represented by the following two structural formulas:

Inorganic / organic block copolymers with inorganic cores, and SiH or olefin ends

, or

Through the embodiments of the present invention, it can be seen that the hybrid material is useful when used in radiation and thermosetting compositions. As used herein, the term “radiation” refers to electromagnetic radiation having energy in the microwave region to the gamma ray region in the electromagnetic spectrum. In addition, a heat energy source and an electron beam energy source may be used to cure the composition of the present invention. The method that can be used for the reaction initiation / curing reaction of the system described below refers to being performed according to the energy used by those skilled in the art and the properties of the initiator known to those skilled in the art.

Furthermore, those skilled in the art will cure the reactive organic / inorganic hybrid copolymer according to the present invention in combination with various additives such as fillers, rheology modifiers, dyes, adhesion promoters and the like. The physical properties of the cured or uncured composition can be adjusted. Illustrative inorganic fillers usable in the present invention include talc, clay, amorphous or crystalline silica, fumed silica, mica, calcium carbonate, aluminum nitride, boron nitride, silver, copper, silver coated copper Solder, and the like, but is not limited thereto. In addition, examples of the polymer filler usable in the present invention include poly (tetrafluoroethylene), poly (chlorotrifluoroethylene), graphite, or poly (amide) fibers. In addition, the flow modifiers usable in the present invention include fumed silica or fluorinated polymers. Moreover, as said adhesion promoter, silane (for example, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-aminopropyl trimethoxysilane, (gamma)-methacryloxypropyl triethoxysilane , β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. In addition, if desired, the copolymer of the present invention may further include a dye and an additive.

Specific practical aspects of the synthesis method according to the present invention will be described by way of examples, but is not limited to the following examples.

Example 1 Synthesis of Tetraallylbisphenol A / TMDS Adduct (1)

A 500 mL round bottom four necked flask was equipped with a reflux cooler, an addition funnel, an internal temperature probe, and a magnetic stirrer and placed under a weak nitrogen flow. The flask was then charged with 1,1,3,3-tetramethyldisiloxane (364 mL, 2.06 mol; “TMDS”; manufactured by Hanse Chemie). The addition funnel was then charged with a mixture of TMDS (5 mL) and tetraallylbisphenol A (20.0 g, 51.5 mmol; “TABPA”; manufactured by Bimax). Then, about 2 mL of the solution was added to the stirred TMDS in the main reaction vessel. The temperature of the reaction vessel was raised to ˜50 ° C., and dichlorobis (cyclooctadiene) Pt (50 ppm Pt, the 2-butanone solution in which the catalyst was dissolved in the amount of 2 mg / mL in the reaction vessel at this temperature). 0.95 mL; manufactured by DeGussa). Then, the internal reaction temperature of the said reaction vessel was raised to -70 degreeC.

And TABPA was added dropwise to the reaction vessel by 25 minutes while maintaining the internal temperature of the reaction vessel below -75 ° C. During the addition reaction, a steady reaction exotherm was observed. After the addition reaction was completed, the reaction was stirred at ˜70 ° C. for 10 minutes. FT-IR analysis showed that allele double bonds were consumed completely, as no C = C stretching bands appearing intensively at wavelengths of 1645 cm ⁻¹ and 1606 cm ⁻¹ .

The reaction was then cooled to below 40 ° C. and excess TMDS was then vacuumed off at this temperature. The TMDS used in this example is a pure material (identified according to GC, ¹ H NMR, and ²⁹ Si assays) and is recyclable. As described above, a pale yellow oil was obtained as a product in quantitative yield. The material was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, GC, MS, GPC, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral characteristics consistent with those exhibited in the structure of the following tetrasilane (1). In addition, analysis of the product according to the GPC analysis confirmed that a single peak with a low polydispersity of 1.2 was obtained (the polydispersity index of the tetraallyl bisphenol reaction initiator was found to be 1.1). On the other hand, as a result of analyzing the product according to the EI-MS analysis, the main molecular ion content is less than expected 924 (calculated molecular ion content of tetrasilane (1) = 924), the molecular ion content of high molecular weight is 999 (tetramethyldi A small amount of hexamethyltrisiloxane present in the siloxane reaction initiator). In addition, the resin was titrated with a resin of 3.84 meq SiH / g, and the theoretical value was 98% (theoretical SiH value = 3.9 meq SiH / g resin; titration of TABPA reaction initiator in 8.4 meq olefin / g resin). Calculated from the olefin content).

Example 2: Synthesis of Tetrafunctional Cycloaliphatic Epoxy Product (1) Radial Siloxane / Hydrocarbon Hybrid Copolymer (2)

In a 250 mL three-necked flask equipped with a magnetic stirrer, internal temperature probe, reflux cooler, and addition funnel, siloxane (1) (Example 1, 8.65 g, 9.35 mmol) was dissolved in toluene (26 mL). Plum blossomed. The reaction vessel was then placed under an appropriate dry nitrogen purge. The addition funnel was charged with vinylcyclohexene oxide (“VCHO”, 4.9 mL, 37.4 mmol). Subsequently, about 0.25 mL of the epoxy was added dropwise to the reaction vessel, and then the temperature of the reactants in the reaction vessel was raised to 50 ° C.

Chlorotris (triphenylphosphine) rhodium (“Wilkinson's catalyst”, 4 mg, 50 ppm based on siloxane mass) was then added to the reaction vessel. And the internal temperature of the said reaction was raised to 65 degreeC, and VCHO was added dropwise. An exothermic reaction was observed during the addition reaction and the reaction was complete after 20 minutes. The internal temperature of the reactants was maintained below 68 ° C. during the addition reaction. The reaction temperature was easily controlled by controlling the rate of addition of VCHO and by heating / cooling the reaction vessel.

After the addition reaction was completed, the reaction was stirred at a temperature of 65 ℃. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) did not appear in the obtained IR spectrum, confirming that the reaction was completed. The reaction was then cooled to room temperature and the activated carbon (˜0.25 g) was slurried with the solution at this temperature for 30 minutes. The solution was then filtered to remove the solvent from the filtrate under vacuum to yield a yellow oil. The material thus obtained was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral properties consistent with those exhibited in the structure of the radial hybrid epoxy compound (2). In addition, the product was analyzed according to the GPC analysis to confirm that a single peak having a low polydispersity of 1.2 was obtained. On the other hand, as a result of analyzing the product according to the EI-MS analysis, the main molecular ion content was 1422 (calculated molecular ion content of the hybrid radial epoxy (2) = 1422) or less, and the molecular ion content of the high molecular weight was 1498 (tetramethyl). A small amount of hexamethyltrisiloxane present in the disiloxane reaction initiator). In addition, it was confirmed that the average epoxy equivalent weight (EEW: epoxy equivalent weight) of the product was 402 (theoretical value 107% calculated from the SiH value for the compound (1) of the 3.9 meq SiH / g resin).

TBPASiCHO-G1-siloxane (2)

Example 2a: Synthesis of Tetrafunctional Cycloaliphatic Epoxy Product (1) Radial Siloxane / Hydrocarbon Copolymer (2) (Other Synthesis Methods)

A 500 mL round bottom four necked flask was equipped with a reflux cooler, an addition funnel, an internal temperature probe, and a magnetic stirrer and then placed under weak nitrogen flow. Then, the flask was charged with siloxane (1) (Example 1, 40.0 g, 43 mmol) solvated in toluene (20 mL). The temperature of the said reaction container filled was raised to -65 degreeC. The addition funnel was charged with vinylcyclohexene oxide (“VCHO”, 21.7 g, 175 mmol). Then, about 3.0 mL of the epoxy was added dropwise to the reaction vessel.

The reaction vessel was then charged with platinum-tetravinylcyclosiloxane complex (Pt-D ^V ₄ “Karstedt catalyst”, 3.5 wt% active Pt ⁰ , 40 ppm Pt ⁰ , 0.046 g based on mass of siloxane (1) Pt complex, manufactured by Gelest).

And VCHO was added dropwise to the reaction vessel for ˜1 hour while maintaining the internal temperature of the reaction vessel below 75 ° C. Normal exothermic reaction was observed during the addition reaction. In addition, the reaction temperature was easily controlled by adjusting the addition rate of VCHO and heating / cooling of the reaction vessel while performing the addition reaction.

After the addition reaction was completed, the reaction was stirred at a temperature of 70 ℃ for 1 hour. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) did not appear in the obtained IR spectrum, confirming that the reaction was completed. The reaction was then cooled to room temperature and the activated carbon (˜0.25 g) was slurried with the solution at this temperature for 1 hour. The solution was then filtered to remove the solvent from the filtrate under vacuum to yield a yellow oil. The material thus obtained was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral properties consistent with those exhibited in the structure of the hybrid epoxy compound (2). In addition, the epoxy equivalent (EEW) of the product was 390 g resin / mol epoxy.

Example 3: Synthesis of Tetraallylbisphenol A / bis (dimethylsilyl) Ethylene Adduct

A 250 mL round bottom four necked flask was equipped with a reflux cooler, an addition funnel, an internal temperature probe, and a magnetic stirrer and then placed under weak nitrogen flow. The flask was then charged with bis (dimethylsilyl) ethane (34.6 g, 514 mmol; “TMDE”; manufactured by Gelest), and then the internal temperature of the reaction vessel was raised to 65 ° C. The addition funnel was charged with tetraallylbisphenol A (20.0 g, 51.5 mmol; "TABPA"; manufactured by Bimax). Then, about 1 mL of the solution was added to the stirred TMDE in the main reaction vessel.

Then chlorotris (triphenylphosphine) rhodium (“Wilkinson catalyst”, 4 mg, ˜40 ppm based on siloxane mass) was added to the reaction vessel.

And TABPA was added dropwise. An exothermic reaction was observed during the addition reaction and the reaction ended after 1 hour. The internal temperature of the reactants was kept below 80 ° C. during the addition reaction. The reaction temperature was easily controlled by controlling the rate of addition of TABPA, and by heating / cooling the reaction vessel. After the addition reaction was completed, the reaction was placed at a temperature of ˜80 ° C. for 30 minutes. FT-IR analysis then confirmed that no C = C stretching bands appearing intensively at wavelengths of 1645 cm ^-1 and 1606 cm ^-1 were observed and the allyl double bond was consumed completely. It was.

The reaction was then cooled to below 40 ° C. and excess TMDE was vacuumed off at this temperature. The TMDE used in this example is a pure material (identified according to ¹ H NMR and ²⁹ Si assays) and is recyclable. As described above, a pale yellow oil was obtained as a product in quantitative yield. The material was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral characteristics consistent with those exhibited in the structure of the tetrasilane (3). The product had a SiH content of 4.31 meq SiH / g resin and a theoretical value of 105%.

Example 4 Synthesis of Tetrafunctional Cycloaliphatic Epoxy Product (1) Radial Silane / Hydrocarbon Copolymer (4)

A 500 mL round bottom four necked flask was equipped with a reflux cooler, an addition funnel, an internal temperature probe, and a magnetic stirrer and then placed under weak nitrogen flow. Then, the flask was charged with siloxane (3) (16.25 g, 16.7 mmol) solvated in toluene (20 mL). The temperature of the said reaction container filled was raised to -65 degreeC. The addition funnel was charged with vinylcyclohexene oxide (“VCHO”, 8.39 g, 67.6 mmol). Then, about 1 mL of the epoxy was added dropwise to the reaction vessel.

The reaction vessel was then Pt ⁰ -tetravinylcyclotetrasiloxane complex (3.5% active Pt ⁰ , 50 ppm Pt ⁰ , 0.232 g Pt ⁰ complex based on the mass of siloxane (3), prepared by Gelest) Was added.

And VCHO was added dropwise to the reaction vessel for ˜1 hour while maintaining the internal temperature of the reaction vessel below 70 ° C. Normal exothermic reaction was observed during the addition reaction. In addition, the reaction temperature was easily controlled by adjusting the addition rate of VCHO and heating / cooling of the reaction vessel while performing the addition reaction.

After the addition reaction was completed, the reaction was stirred at a temperature of 75 ℃ for 1 hour. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) did not appear in the obtained IR spectrum, confirming that the reaction was completed. Then 0.5 g of each VCHO, and Pt ⁰ -catalyst (0.007 g of catalyst solution) were further added to the reaction. The reaction was further stirred at 75 ° C. for 30 minutes, and then no SiH band appeared in the IR spectrum obtained by FT-IR analysis, confirming that the reaction was complete. The reaction was cooled to room temperature and activated carbon (˜3.0 g) was slurried with the solution at this temperature for 1 hour. The solution was then filtered to remove the solvent from the filtrate under vacuum to yield a yellow oil. The material thus obtained was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral properties consistent with those exhibited in the structure of the following hybrid epoxy compound (4). In addition, the epoxy equivalent (EEW) of this product was 430 g resin / mol epoxy.

TBPASiCHO-G1-silane (4)

Example 5: Synthesis of Tetrafunctional Glycidyl Epoxy Product (1) Radial Siloxane / Hydrocarbon Copolymer

In a 100 mL three-necked flask equipped with a magnetic stirrer, internal temperature probe, reflux cooler, and addition funnel, siloxane (1) (Example 1, 3.00 g, 3.24 mmol) was dissolved in toluene (5 mL). Plum blossomed. The reaction vessel was then placed under an appropriate dry nitrogen purge. Then, allyl glycidyl ether (“AGE”, 1.48 g, 13.0 mmol) was dissolved in toluene (5 mL), and then charged into the addition funnel. Subsequently, about 0.25 mL of the epoxy was added dropwise to the reaction vessel, and then the temperature of the reactants in the reaction vessel was raised to 60 ° C.

To the reaction vessel was then added Pt-D ^V ₄ complex (3.5 wt% active Pt ⁰ , 50 ppm Pt ⁰ , 0.042 g Pt complex, manufactured by Gelest based on the mass of siloxane (1)) .

And the said AGE was added dropwise to the said reaction container for 10 minutes, maintaining the internal temperature of the said reaction container below 80 degreeC. Some exothermic reaction was observed during the initiation of the addition reaction. After the addition reaction was completed, the reaction was stirred at a temperature of 80 ℃ for 5 hours. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) did not appear in the obtained IR spectrum, confirming that the reaction was completed. The reaction was then cooled to room temperature and the activated carbon (˜0.5 g) was slurried with the solution at this temperature for 1 hour. The solution was then filtered and the solvent was removed in vacuo from the filtrate to give a yellow oil (4.48 g, 85%). The product thus obtained was found to exhibit spectral properties consistent with those exhibited in the structure of the following hybrid epoxy compound (5). In addition, the epoxy equivalent (EEW) of this product was 422 g resin / mol epoxy.

TBPASiGE-G1-siloxane (5)

Example 6: Synthesis of diallyl ether bisphenol A / TMDS adduct (6)

A 500 mL volume round bottom four necked flask was equipped with a reflux condenser, addition funnel, internal temperature probe, and magnetic stirrer. The flask was charged with 1,1,3,3-tetramethyldisiloxane (573 mL, 3.25 mol; “TMDS”; manufactured by Hanse Chemie). The temperature of the said reaction container filled was raised to -65 degreeC. The addition funnel was charged with diallyl ether bisphenol A (50 g, 0.162 mol "DABPA"; manufactured by Bimax S). Then, about 5 mL of DABPA was added to the stirred TMDS in the main reaction vessel. Then, dichlorobis (cyclooctadiene) Pt ^∥ to the reaction vessel; was added (40 ppm Pt, the catalyst was 2 mg / mL of 2-butanone solution of 1.9 mL dissolved in the amount of production in the DeGussa).

After the solution was added, the TABPA was added dropwise to the reaction vessel for about ˜25 minutes, and when the TABPA was slowly added dropwise, a slight exothermic reaction appeared. After the addition reaction was completed, the reaction was stirred for 10 minutes at a temperature of ~ 70 ℃. FT-IR analysis showed no C = C stretching bands appearing concentrated at a wavelength of 1648 cm ⁻¹ , confirming that the allyl double bond was consumed completely. And, the dichlorobis (cyclooctadiene) Pt ^∥ (20 ppm Pt, the catalyst solution of 1.0 mL) was added. Then, booster catalyst was added, resulting in some exothermic reaction. The reaction was left at a temperature of 70 ° C. for 1 hour. FT-IR analysis then confirmed that the reaction was not complete, and further added dichlorobis (cyclooctadiene) Pt ^∥ (30 ppm Pt, 1.4 mL of catalyst solution) to the solution. 10 minutes after the addition of the catalyst solution, the FT-IR analysis confirmed that the reaction was completed.

The reaction was then cooled to below 40 ° C. and excess TMDS was then vacuumed off at this temperature. The TMDS used in this example is a pure material (identified according to ¹ H NMR and ²⁹ Si assays) and is recyclable. As described above, yellow oil was obtained as a product in quantitative yield. The material was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral properties consistent with those exhibited in the structure of the following "hybrid siloxane" (6). In addition, the product was analyzed according to the GPC analysis to confirm that a single peak having a low polydispersity of 1.2 was obtained. On the other hand, as a result of analyzing the product according to the EI-MS analysis, the primary molecular ion content was less than the expected 576.7 (calculated molecular ion content of the bis (silane) (6) = 576.5), the molecular ion content of the high molecular weight is 650 ( A small amount of hexamethyltrisiloxane present in the tetramethyldisiloxane reaction initiator).

Hybrid siloxane (6)

Example 7: Synthesis of Bifunctional Cyclic Aliphatic Epoxy Product (1) Linear Siloxane / Hydrocarbon Copolymer (7)

Hybrid siloxane (6) (28.7 g, 50 mmol) was solvated in toluene (10 mL) in a 250 mL volume three-necked flask equipped with a magnetic stirrer, internal temperature probe, reflux cooler, and addition funnel. The addition funnel was then charged with vinylcyclohexene oxide (“VCHO”, 13.34 mL, 103 mmol). The temperature of the reactants in the reaction vessel was then raised to 75 ° C. and about 0.50 mL of the epoxy was added dropwise to the reaction vessel. Immediately thereafter, 2-butanone in which about 20 ppm of Pt and the catalyst complex were dissolved in an amount of 2 mg / mL based on the mass of dichloro-bis (cyclooctadiene) Pt (hybrid siloxane (6)) in the reaction vessel. 0.5 mL of solution) was added. And VCHO was added dropwise. An exothermic reaction was observed during the addition reaction and the reaction was complete after 20 minutes. The internal temperature of the reactants was kept below 80 ° C. during the addition reaction. The reaction temperature was easily controlled by controlling the rate of addition of VCHO and by heating / cooling the reaction vessel.

After completion of the addition reaction, the reaction was stirred for 5 minutes at a temperature of 80 ℃. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) did not appear in the obtained IR spectrum, confirming that the reaction was completed. The reaction was then cooled to room temperature and the activated carbon (˜1.0 g) was slurried with the solution at this temperature for 2 hours. The solution was then filtered to remove the solvent from the filtrate under vacuum to yield a yellow oil. The material thus obtained was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, EI-MS, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral properties consistent with those exhibited in the structure of the following hybrid epoxy compound (7). In addition, the product was analyzed according to GPC analysis, and it was confirmed that a single peak having a polydispersity of 1.7 was obtained. On the other hand, as a result of analyzing the product according to the EI-MS analysis method, the main molecular ion amount was expected 825 (calculated molecular ion content of the hybrid epoxy (7) = 825). In addition, the average epoxy equivalent (EEW) of the product was found to be generally about 498 g resin / mol epoxy.

Linear Organic / Inorganic Hybrid Cycloaliphatic Epoxy (7)

Example 8: Synthesis of Bifunctional Glycidyl Epoxy Product (1) Siloxane / Hydrocarbon Hybrid Copolymer (8)

In a 250 mL three-necked flask equipped with a magnetic stirrer, internal temperature probe, reflux cooler, and addition funnel, siloxane (6) (31.0 g, 53 mmol) was solvated in toluene (10 mL). The addition funnel was then charged with allyl glycidyl ether (“AGE”, 15.77 mL, 134 mmol). The temperature of the reactants in the reaction vessel was then raised to 75 ° C. and about 0.50 mL of the epoxy was added dropwise to the reaction vessel. Immediately thereafter, in the reaction vessel, Pt ⁰ -tetravinylcyclotetrasiloxane complex (3.5% active Pt ⁰ , about 14 ppm Pt ⁰ based on the mass of the compound (6), 0.124 g of Pt complex, Gelest Preparation) was added. And the said AGE was added dropwise. An exothermic reaction was observed during the addition reaction and the reaction ended after 30 minutes. The internal temperature of the reactants was kept below 80 ° C. during the addition reaction. The reaction temperature was easily controlled by controlling the rate of addition of the AGE, and by heating / cooling the reaction vessel.

After the addition reaction was completed, the reaction was stirred at a temperature of 75 ℃. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) was present in the obtained IR spectrum, confirming that the reaction was not completed. Subsequently, further addition of the catalyst at a charge of 7 ppm (0.062 g of Pt ⁰ complex) resulted in an exothermic reaction and reduced IR absorption band strength of SiH. The catalyst was then added twice or more at 10 minute intervals each (0.030 g of Pt ⁰ complex, in amounts of about 3 ppm each). Then, FT-IR analysis showed that no SiH band was observed, confirming that the reaction of the reactant was terminated. The reaction was then cooled to room temperature and the activated carbon (˜1.0 g) was slurried with the solution at this temperature for 2 hours. The solution was then filtered to remove the solvent from the filtrate under vacuum to yield a yellow oil. The material thus obtained was analyzed according to ¹ H, ²⁹ Si, and ¹³ C NMR, GPC, MS, and FT-IR analysis. As a result, it was confirmed that the product exhibited spectral properties consistent with those exhibited in the structure of the following hybrid epoxy compound (8). In addition, the product was analyzed according to GPC analysis, and it was confirmed that a single peak having a low polydispersity (1.2) was obtained. On the other hand, when the product was analyzed according to the EI-MS analysis method, the primary molecular ion amount was expected 804 (calculated molecular ion amount value of the hybrid epoxy (8) = 806). In addition, the average epoxy equivalent (EEW) of the product was found to be about 590.

Linear Organic / Inorganic Hybrid Glycidyl Epoxy (8)

Example 9 Synthesis of Radial Hybrid Copolymer Having α-methyl Styrene Termination

A 250 mL round bottom four necked flask was equipped with a reflux condenser, addition funnel, internal temperature probe, and magnetic stirrer. The flask was charged with 1,3-diisopropenylbenzene (300 mL, 2.04 mol; manufactured by Cytec), and then the internal temperature of the reaction vessel was raised to 65 ° C. In addition, siloxane (1) (15.00 g, 16.20 mmol) was solvated in 1,3-diisopropenylbenzene (200 mL, 1.36 mol) and then charged into the addition funnel. Then, at an internal temperature of 65 ° C. of the reaction vessel, Pt ⁰ -tetravinylcyclotetrasiloxane complex (3.5% active Pt ⁰ , 85 ppm Pt ⁰ , based on the mass of compound (1), was added to the reaction vessel. Immediately after addition of 0.042 g of Pt complex, manufactured by Gelest), ~ 4 mL of siloxane (1) solution was added. No exothermic reaction occurred during the addition reaction. The internal temperature of the reaction vessel was raised to 70-75 ° C., and then the solution of siloxane (1) was added to the reaction vessel for 15 minutes. The reaction was then left for 4 hours at a temperature of 70-75 ° C. Subsequently, as a result of performing FT-IR analysis, it was confirmed that the SiH band (2119 cm ⁻¹ ) did not exist in the obtained IR spectrum, indicating that the reaction was completed. After confirming that the reaction was complete, the reaction was cooled to room temperature, and activated carbon (˜0.5 g) was slurried with the solution at this temperature for 1 hour. The solution was then filtered and the solvent was removed in vacuo from the filtrate to give a yellow oil compound (9) (23.5 g, 95%). The radial hybrid copolymers thus obtained were analyzed according to ¹ H, ¹³ C, and ²⁹ Si NMR, and FT-IR analysis:

Radial Hybrid Copolymer-G2 with α-Methyl Styrene Termination (9)

Example 10 Synthesis of Radial Hybrid Copolymers Having Secondary Product SiH-terminus

A 250 mL round bottom four necked flask was equipped with a reflux cooler, an addition funnel, an internal temperature probe, and a magnetic stirrer and then placed under weak nitrogen flow. Then, the flask was charged with 1,1,3,3-tetramethyldisiloxane (100 mL, 565 mmol; “TMDS”; manufactured by Hanse Chemie), and then the internal temperature of the reaction vessel was raised to 65 ° C. I was. Hybrid copolymer 9 (11.0 g, 7 mmol) having olefinic ends was solvated in TMDS (50 mL, 282 mmol) and then added slowly to the addition funnel to charge. Then, when the internal temperature of the reaction vessel reached 65 ° C., 50 ppm of Pt ⁰ based on the mass of Pt ⁰ -D _v ⁴ complex (3.5% active Pt ⁰ , compound (9)) in the reaction vessel , 0.018 g of Pt complex, manufactured by Gelest), immediately after addition of 4 mL of the copolymer (9) -TMDS solution was added. At this time, a solution of the copolymer 9 was added to the reaction vessel for 15 minutes. After the addition reaction was completed, the temperature of the reactant was raised to 70-75 ° C. for 2 hours. The reaction was then cooled to room temperature and the activated carbon (˜0.5 g) was slurried with the solution at this temperature for 2 hours. The solution was then filtered and the solvent was removed in vacuo from the filtrate to give a yellow oil compound (12.7 g, 95%). The material thus obtained was analyzed according to ¹ H, ¹³ C, and ²⁹ Si NMR, and FT-IR spectroscopy, whereby the product had a structure of radial organic / inorganic hybrid copolymer 10 having the following SiH terminus. It was found to exhibit spectral properties consistent with the properties exhibited. In addition, the SiH titer of the copolymer was found to be 2.35 meq SiH / g resin.

Radial Hybrid Copolymer-G2 with SiH Termination (10)

Example 11: Synthesis of Tetrafunctional Cycloaliphatic Epoxy Product (2) Radial Siloxane / Hydrocarbon Hybrid Copolymer (11)

A 500 mL round bottom four necked flask was equipped with a reflux cooler, an addition funnel, an internal temperature probe, and a magnetic stirrer and then placed under weak nitrogen flow. The flask was then charged with radial copolymer 10 (12.0 g, 5.72 mmol) solvated in toluene (20 mL). The temperature of the said reaction container filled was raised to -65 degreeC. The addition funnel was charged with vinylcyclohexene oxide (“VCHO”, 2.84 g, 22.87 mmol). Then, about 1 mL of the epoxy was added dropwise to the reaction vessel.

To the reaction vessel was then added Pt ⁰ -D _v ⁴ complex (3.5% active Pt ⁰ , 35 ppm Pt ⁰ , 0.014 g of Pt complex, manufactured by Gelest based on mass of compound (10)). .

And VCHO was added dropwise to the reaction vessel for ˜1 hour while maintaining the internal temperature of the reaction vessel below 70 ° C. Normal exothermic reaction was observed during the addition reaction. In addition, the reaction temperature was easily controlled by adjusting the addition rate of VCHO and heating / cooling of the reaction vessel while performing the addition reaction.

After the addition reaction was completed, the reaction was stirred at a temperature of 70 ℃ for 2 hours. Then, FT-IR analysis showed that the SiH band (2119 cm ^-1 ) did not appear in the obtained IR spectrum, confirming that the reaction was completed. The reaction was then cooled to room temperature and the activated carbon (˜1.0 g) was slurried with the solution at this temperature for 2 hours. The solution was then filtered and the solvent removed from the filtrate under vacuum to give a yellow oil (13.6 g, 92%). The material thus obtained was analyzed according to ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR, and FT-IR spectrometry, and the spectral properties of the product were consistent with those exhibited in the structure of the radial hybrid epoxy compound (11) as follows. It was confirmed to represent. In addition, the epoxy equivalent (EEW) of this resin was 573 g resin / mol epoxy.

TBPASiCHO-G2 (11)

Example 12 Synthesis of Hybrid Radial Copolymers having G1-olefin Terminations Using Inorganic Cores.

Dicyclopentadiene (“DCPD”, 40 eq.) Was solvated in toluene under purge of dry air in a round bottom flask equipped with an addition funnel, reflux cooler, magnetic stirrer, and internal temperature probe. The addition funnel was then charged with tetrakis (dimethylsilyl) siloxane (“TDS”, 1 eq.). Subsequently, the temperature of the solution in the reaction vessel was raised to 50 ° C., and then dichloroplatinum bis (dicyclopentadiene) (Cl ₂ PtCOD ₂ , 20 ppm based on the mass of TDS) was added to the solution at the temperature. It was. The internal temperature of the reaction vessel was raised to 70 ° C. and then TDS was added dropwise to the reaction while maintaining the internal temperature below 80 ° C. After the addition reaction was completed, the solution was stirred at the temperature for 10 minutes, and FT-IR analysis was performed at this temperature, and it was confirmed that the SiH functional group was completely consumed. The excess DCPD and toluene were then removed in vacuo to give a pale yellow oil (12) having the structure

Example 13: Synthesis of Hybrid Radial Copolymer with Inorganic Core and G1-SiH Termination

A 500 mL four-necked flask equipped with a mechanical stirrer, reflux condenser, addition funnel, and internal temperature probe was subjected to 1,1,3,3-tetramethyldisiloxane (“TMDS”, 40 eq.) Was charged. Then, the addition funnel was charged with the compound (12) (1 eq.). The reaction vessel was then placed in an oil bath and heated to an internal temperature of 50 ° C. Then, Cl ₂ Pt (COD) ₂ (20 ppm based on the mass of the compound (12)) was added to the reaction vessel, and the internal temperature was raised to 75 ° C. Then, the compound (12) was added dropwise to the reaction vessel for 30 minutes while maintaining the internal temperature of the reaction vessel at 75 to 85 ° C. After the addition reaction was completed, the reaction was stirred for 20 minutes at a temperature of 80 ℃. Then, the excess TMDS was removed in vacuo and then regenerated to obtain Compound (13), which is a pale yellow oil represented by the following structural formula:

(13)

.

Example 14 Synthesis of Hybrid Radial Copolymers with Inorganic Cores and G1-cyclic Aliphatic Epoxy Terminations.

Compound (13) (1 eq.) Was dissolved in toluene (50 wt.% Solution) under a purge of dry air in a 500 mL volume round bottom four-necked flask equipped with a mechanical stirrer, an addition funnel, and an internal temperature probe. Plum blossomed. The addition funnel was then charged with vinylcyclohexene oxide (“VCHO”, 4 eq.). The temperature of the reaction vessel was then raised to 50 ° C. and then Cl (PPh ₃ ) ₃ Rh (20 ppm based on the mass of compound 13) was added to the solution at this temperature. The internal temperature of the reaction vessel was raised to 70 ° C., and then the VCHO was added dropwise to the reactant for 20 minutes while maintaining the internal temperature below 80 ° C. After the addition reaction was completed, the solution was stirred at a temperature of 75 ° C. for 10 minutes, at which time, the FT-IR spectral analysis was performed on the reaction mixture, and the starting material at a wavelength of 2120 cm ⁻¹ was obtained. It was confirmed that there was no band corresponding to the SiH functional group of 13) at all. Then, the solvent was removed in vacuo to give product 14, which is a pale yellow oil represented by the following structural formula:

(14)

Example 15 Comparison of DVS Water Uptake of Hybrid Epoxy and Conventional Hydrocarbon Epoxy Resin.

For the cured material sample, the saturated water vapor absorption at a temperature of 85 ° C. and a relative humidity of 85% was measured, and dynamic DV adsorption (DVS) was calculated therefrom to compare the DVS values. , Hydrophobicity of the fully cured material was evaluated. Various epoxy resins used in this test were formulated using 1% by weight of cationic photo / thermal curing reaction initiator iodonium salt Rhodorsil 2074 (manufactured by Rhodia), cast in a 1 mm thick mold, and then at a temperature of 175 ° C. Cured at 1 hour. Each sample cured as described above was placed in a chamber of the test DVS apparatus and then tested until the absorption (mass increase) of water vapor was stopped. In addition, the main results obtained by performing the test are summarized in Table 1.

From the data shown in Table 1, the hybrid epoxy absorbs much less water than the typical hydrocarbon epoxy in saturation, and thus has high hydrophobicity compared to such conventional carbon-based epoxy resins (EPON 828 and ERL 4221). It can be seen that. It can also be seen that the radial tetrafunctional hybrid epoxies 2 and 4 have slightly greater hydrophobicity than similar linear bifunctional analogs 7 and 8.

Table 1: Saturated Water Vapor Uptake Comparison

Example 16: Thermal Stability Comparison of the Hybrid Epoxy of the Invention with Commercially Available Epoxy Resins

The thermal stability of the hybrid resins of the present invention and conventional commercially available hydrocarbon epoxy materials were tested and compared. Each sample was analyzed in an uncured liquid material and in a cured solid material state. At this time, the cured product sample was obtained by formulating various resins including Rhodorsil 2074 (Rhodia), which is 0.5% by weight of cationic thermal curing / photocuring initiator, and then curing for 1 hour at a temperature of 175 ° C. Then, the TGA analysis was performed by raising the temperature of each cured product and the uncured sample according to a temperature of 30 ° C. to 300 ° C. and a heating profile having a heating rate of 20 ° C./min, and then maintaining the temperature at 300 ° C. for 30 minutes. It was. As a result of the TGA analysis as described above, the temperature at which 1% and 10% mass loss occurs in each material, and the total mass loss seen in each sample when the thermal profile was completely terminated is shown in Table 2.

Table 2: Comparison of TGA Analysis of Radial Hybrid and Hydrocarbon Epoxy

The results shown in Table 2 show that the radial hybrid epoxy resins (both uncured and cured) exhibit significantly improved thermal stability compared to conventional commercially available hydrocarbon analogs. The thermal stability improvement of the radial hybrid epoxy resin is due to the inorganic nature of the siloxane or silane ratio / block of the hybrid material.

Example 17 Compatibility of Hybrid Epoxy of the Invention with Commercially Available Hydrocarbon Resin and Siloxane Resins

The compatibility of a representative radial hybrid epoxy (2) with the corresponding appropriate hydrocarbon resin and siloxane resin was tested. The compatibility of the resin was qualitatively analyzed by evaluating the transparency of the initially formed mixture and the stability of the once formed mixture. The results are shown in Table 3. In the table below, each blend is expressed in weight percent.

Table 3: Miscibility of Radial Hybrid Epoxy of the Invention with Hydrocarbon Resin and Siloxane Resin

From the results shown in Table 3, it can be seen that the radial hybrid epoxy (2) shows compatibility with various hydrocarbon resins such as ERL-4221 and CHVE from a macroscopic viewpoint. In addition, the radial hybrid epoxy (2) it can be seen that high compatibility with the siloxane resin, such as a siloxane resin Sycar ^®. The mixture of Epon 828 and up to 10% by weight of the hybrid was somewhat opaque, but no bulk phase separation was observed at room temperature (or after performing a subsequent curing process). Also, from the remarks of the last item in the classification of the table above, commercially available conventional epoxysilane EMS-232 (product obtained by hydrosilylation of a conventional methylhydrodimethylsiloxane copolymer and vinyl cyclohexene oxide, Gelest) When left for a few days at room temperature, it can be seen that bulky phase separation reaction of the epoxysilane occurred from hydrocarbon epoxy such as Epon 828.

Example 18 Flexibilization of UV and Heat Cured Formulations (Epon 828 + Copolymer of the Invention)

Since various hybrid epoxy resins of the present invention exhibit improved compatibility with hydrocarbon-based materials, they can be usefully used to impart flexibility to conventional epoxy thermosets. Thus, a blend of Epon 828 and the hybrid epoxy 2 in some proportion was prepared. 1% by weight of a cationic polymerization initiator (Rhodorsil 2074 iodonium salt) was added to the blend thus obtained, and then cast into a film having a wet thickness of about 10 mil using a drawdown bar. This was cured at 175 ° C. for 1 hour. The cured film was then analyzed according to dynamic mechanical analysis (DMA) (Ares RSA, frequency: 1 Hz, 100 ° C to 250 ° C) to obtain modulus according to temperature and T _g . It was. The analysis results are shown in Table 4.

From the data obtained through the above analysis, as the amount of the hybrid epoxy 2 (TBPASiCHO-G1-siloxane) is relatively increased, the elastic modulus (E ') of each film at a temperature below T _g is increased. It can be confirmed that the degradation. In addition, as the amount of the hybrid epoxy 2 is relatively increased, it can be seen that the T _g of the cured matrix is also lowered. In addition, it can be seen from the T _g observed in each of the above blends that each material has uniformity from a macroscopic point of view. It can be seen that when a phase separation reaction occurs (e.g., when phase separation occurs due to poor miscibility of the hybrid epoxy component and hydrocarbon), two T _g values appearing in two homopolymer networks are obtained. have.

Accordingly, various hybrid epoxys of the present invention, such as compound (2), can be used to impart flexibility to conventional hydrocarbon epoxy matrices. This is possible because the hybrid copolymers of the present invention have improved organic miscibility and the inherent flexibility is imparted to the compounds by the inorganic siloxane segments of the material.

Table 4: DMA Analysis of Hydrocarbon / Hybrid Epoxy Blends

Epoxy / blend ~ E '(x10 ^-9 kPa) at 50 ° C ~ E '(x10 ^-9 kPa) at 25 ° C ˜T _g (° C.) 100% Epon 828 2.1 2.0 190 Epon 828: ( 2 ), blend ratio 95: 5 2.0 1.8 180 Epon 828: ( 2 ), blend ratio 90:10 1.5 1.0 165 100% TBPASiCHO-G1-siloxane 1.1 1.0 80

Example 19 Cationic UV Curing of Radial Hybrid Epoxy (2)

The cyclic aromatic of Example 2, with 1% by weight of iodonium borate Rhodorsil 2074 (0.03 g, Rhodia) as a cationic polymerization photoinitiator, and 0.0075 g of isopropyl thioxanthone (equal molar amount with the Rhodorsil photoinitiator, manufactured by First Chemical) Epoxysilane (TBPASiCHO-G1-siloxane ( 2 ), 3.0 g) was formulated. The preparation sample (2.1 mg) thus obtained was analyzed by DPC (differential photocalorimetry, “photoDSC”), and the analysis results are shown in FIG. 1.

The formulation cured much faster than the epoxy cured by conventional cationic curing reactions, and an exothermic peak was observed 0.13 minutes after the curing reaction was initiated in the curing reaction of the formulation. Even at low intensity conditions in the device photoDSC used in the assay, the conversion rate of the formulation system was about 56%, and the conversion ratio was calculated based on the photopolymerization enthalpy (-147 J / g) of the formulation.

Example 20 Acceleration of UV Curing Reaction of Conventional Glycidyl Epoxy (Epon 828)

Three formulations were prepared as follows:

Formulation 1: Epon 828 (Shell) + 1% by weight of Rhodorsil 2074 (Rhodia)

Formulation 2: Radial Hybrid Epoxy (2) + 1 wt .-% Rhodorsil 2074

Formulation 3: Blend obtained with a blend ratio of hybrid epoxy (2): Epon 828 at 10:90 + 1% by weight of Rhodorsil 2074.

The three formulations were analyzed using DPC (“photoDSC”). As is known to those skilled in the art, the glycidyl epoxy (formulation 1) exhibits a wide range of exothermic reactions upon curing, therefore, the UV curing reaction rate is not good (times with the highest exothermic peak-0.8 minutes). UV curing conversion is relatively low (-34%). On the other hand, the radial hybrid epoxy (2) (the second agent) had a good UV curing reaction rate (a sharp exothermic peak, a time at which the exothermic peak was the highest-0.13 minutes), and a good curing conversion rate during the UV curing reaction, as in the result of Example 19. (-> 60%) is shown. The blend obtained by blending the two epoxies described above at a ratio of 10:90 w / w (Preparation 3) has a sharp exothermic peak (time at which the exothermic peak is the highest-0.13 minutes), and an appropriate curing conversion rate (-) upon irradiation with UV rays. 45%). The results of this example are shown in FIG. Therefore, a small amount of the radial hybrid epoxy according to Example 2 can be blended with a conventional hydrocarbon epoxy (such as Epon 828) to greatly improve the UV curing reaction rate and conversion rate. This is possible because the hybrid epoxy resin of the present invention has improved miscibility compared to the epoxy silane according to the prior art.

Example 21 Cationic UV Curing Reaction of Hybrid Epoxy (2) / Vinyl Ether Blend

Since the said hybrid epoxy is generally excellent in miscibility with a hydrocarbon, it can mix and use other reactive material (not other epoxy only). Thus, the radial hybrid epoxy (2) was formulated by mixing with CHVE (ISP), and UV9380C cationic polymerization initiator (GE Silicones) in the following amounts:

Radial hybrid epoxy (2): 88.5 parts by weight

CHVE: 10 parts by weight

UV9380C: 1.5 parts by weight.

As a result of analyzing the preparation by using photoDSC, it was confirmed that the reactivity was high when the preparation was UV cured. PhotoDSC analysis data of the formulation is as shown in FIG. 3. The peak time of the exothermic peak was 0.13 min, and the polymerization enthalpy of the formulation was determined to be 198 J / g, and the conversion obtained based on the enthalpy reached about 70%, even though the light intensity in the photoDSC was low. (-22 mW / cm 2 broadband irradiation degree). The cured film of the formulation was transparent, which shows that no macroscopic phase separation reaction occurred, and that the radial hybrid epoxy and the CHVE vinyl ether had excellent miscibility.

Example 22 Curing Composition of an Amine Including Radial Hybrid Epoxy (5)

The hybrid epoxy of the present invention can be cured using various curing agents known in the art. For example, the radial hybrid glycidyl type epoxy (5) was mixed with 5% by weight of diethylenetriamine (DETA) and then thermally cured in a DSC apparatus. The amount of curing calorific value obtained in this way was large and exhibited the highest calorific value at 139 ° C. when the formulation was heated at a rate of 10 ° C./min. In addition, the polymerization enthalpy of the above formulation was 268 J / g. Analysis results according to the present embodiment are as shown in FIG. 4.

Example 23 Cationic Thermoset Reaction of Radial Hybrid Epoxy (2)

The hybrid cyclic aliphatic epoxy of Example 2 was blended with 1% by weight of Rhodorsil 2074 (Rhodia) to prepare a clear formulation. The mixture was heat cured in a DSC device (note that in general, iodonium salts can be used as cationic thermal initiators, in addition to photoinitiators). As shown in FIG. 5, as a result of using the formulation, a wide range of cation curing reactions were observed (polymer enthalpy = 214 J / g), and the temperature at which the exothermic reaction was the highest was 143 ° C.

Example 24 UV Curable Compositions Comprising a Radial Hybrid Copolymer 9 Having an Olefin End, and Liquid Maleimide Resin

Hybrid radial copolymers having olefinic ends of the present invention can be used as reactive resins, according to various methods known to those skilled in the art. Accordingly, polymerization or copolymerization of such unsaturated hybrid copolymers can be carried out using conventional radial or cationic thermal initiators or photoinitiators. For example, "electron-rich" (electron-acceptable) olefinic materials (e.g. maleimide) can be employed using various olefins (e.g., electron-donating) various olefins (e.g. vinyl ether, vinyl amide, or styrene derivatives) , Fumarate esters, or maleate esters) are known to be effectively carried out.

Thus, the radial hybrid copolymer 9 having the olefinic end of Example 9 was used in an equimolar (the same molar electron donating and electron accepting double bond) liquid bismaleimide (Example B of US Pat. No. 6,256,530). And 2% by weight of Irgacure 651 (Ciba Specialty Chemicals) as photoinitiator. The formulation thus obtained was analyzed by DPC (“photoDSC”). The results of the analysis are shown in FIG. 6, and when the light is irradiated with the amount of emission emitted from the medium pressure mercury lamp used in the photoDSC device, it is quick and accurate (time of exothermic peak = 0.11). Min), a wide range (photopolymerization enthalpy = 142 J / g) can be seen that the photocuring reaction is carried out.

Example 25: A thermosetting composition comprising a radial hybrid copolymer 9 having an olefin end and a liquid maleimide resin

A thermal curing agent may be used in place of the photoinitiator component to thermally cure the “electron donating / electron accepting formulation” of Example 24. Accordingly, the preparation was prepared in the same manner as in Example 24, except that 2% by weight of USP90 MD peroxide (Witco) was used as the thermal initiator instead of Irgacure 651, which is a photoinitiator. The mixture thus obtained was cured in a DSC apparatus. The results of analyzing the formulations are as shown in FIG. 7, and from the diagrams shown in FIG. 7, it was confirmed that the result of using the formulations was rapid and extensive thermal polymerization.

Example 26 Cationic Thermoset Reaction of Radial Hybrid Copolymer 9 Having Olefin Ends

The radial hybrid copolymer 9 was formulated with 2% by weight of iodonium borate salt Rhodosil 2074. The formulation was then thermally cured in a DSC apparatus to obtain data, and the data analysis results are shown in FIG. 8 (the iodonium borate salt is effective as a thermal initiator (as well as a photoinitiator) in a cationic polymerization reaction). . From the analytical data it can be seen that the formulation has been polymerized extensively and its polymerization enthalpy is 386 J / g. In addition, a bimodal exothermic reaction was observed, but its origin is unknown at present.

Example 27 Use of Tetrasilane (3) as Crosslinking Agent for Addition Cure Thermoset

The SiH functional intermediates described herein can be used as components of a thermosetting system in hydrosilylation cure reactions. For example, tetrasilane (1) can be used as a hardening | curing agent of vinyl siloxane resin. A formulation was prepared as follows and analyzed by DSC (thermal ramping rate: 10 ° C./min) to confirm that a rapid and extensive curing reaction occurred. Analysis results according to the present embodiment are as shown in FIG. 9.

Formulation:

Poly (dimethylsiloxane) with vinyl end (DMS-V05, Gelest): 4.0 g

(About 5.19 mmol of vinyl functional groups)

Tetrasilane (1): 2.4 g (about 5.19 mmol of SiH functional group)

Pt ⁰ -D ^v ₄ catalyst solution: 0.01 g (50 ppm Pt, SIP 6832.0, Gelest)

The mixture was gelled at rt for 15 min. Those skilled in the art know that various curing profiles and physical properties can be obtained by properly selecting vinylsiloxane and hydroxylsiloxane resins as catalysts, catalyst levels, inhibitors, and substrates, and by properly formulating these addition curing silicone systems. Can be.

Example 28 UV Curable Coatings / Sealts Comprising Radial Hybrid Epoxy (2)

The basic UV curable mixture was formulated as follows:

Formulation 28-1: Radial Hybrid Epoxy (2): 8.0 g

CHVE (ISP): 2.0 g

Rhodorsil 2074 (Rhodia): 0.1 g

Isopropyl thioxanthone (ITX): 0.05 g

Using a drawdown bar, a 5 mil thick film (film on PTFE coated aluminum) was formed. Then, the film was cured by using a Dymax fixed UV curing unit (UVA dose ~ 550 mJ / cm 2, 100 W mercury arc lamp) to obtain a solid film, and then the PTFE coated substrate was removed from the film. . Then, using a Permatran 3/33 device (Mocon, Inc.), the moisture barrier property of the film was measured at a temperature of 50 ° C. and a relative humidity of 100%. As a result, the water vapor transmission coefficient was found to be 21.9 g · mil / 100 in ² · 24 h. Thus, the resin system of Formulation 28-1 does not need to perform a thermal curing process subsequently, and can be used as a moisture barrier coating or sealant in which the UV curing reaction is performed quickly.

Example 29 UV Curable Coatings / Sealants with Radical Hybrid Epoxy (2) Filled with High Contents

The following resin system was blended with talc filler:

Formulation 29-1: Radial Hybrid Epoxy (2): 8.0 g

CHVE (ISP): 2.0 g

9380C Iodonium Salt Photoinitiators (GE silicones): 0.2 g

FDC Talc (Luzenac Americas): 6.7 g

By manually mixing the resin / filler system and then passing it through two in three roll mills, the filler particles could be completely blended out with the resin components. The formulation was then briefly degassed (P-25 Torr). A drawdown bar was used to form a 5 mil thick film (film on PTFE coated aluminum). The film was cured by using a Dymax fixed UV curing unit (UVA dose-550 mJ / cm 2, 100 W mercury arc, etc.) to obtain a solid film, and then the PTFE-coated substrate was removed from the film. And the moisture barrier property of the said film was measured using the Permatran 3/33 apparatus (Mocon, Inc.) at the temperature of 50 degreeC and 100% of the relative humidity. As a result, the water vapor transmission coefficient was found to be 12.1 g · mil / 100 in ² · 24h. The water vapor permeability of the base formulation is at a level commercially available as a sealant for sealing the periphery of organic light emitting diode (OLED) devices. In addition, it can be seen that due to the property that the resin system has high reactivity, it is effective to UV cure 5 mil thick and high content filled films.

Example 30 Use of Adhesive Compositions of Copolymers Having Hybrid Epoxy Terminations

The resin system as shown below was produced and the usefulness of the hybrid epoxy resin of this invention was confirmed in both a UV curable adhesive and a thermosetting adhesive use.

Formulation 30-1: Radial Hybrid Epoxy (2): 9.0 g

CHVE (ISP): 1.0 g

9380C Iodonium Salt Photoinitiator (GE silicones): 0.2 g

Cabosil TS-720 (Cabot): 0.1 g

Formulation 30-2: Epon 828: 10.0 g

9380C iodonium salt initiator: 0.2 g

Cabosil TS-720 (Cabot): 0.1 g

Using two formulations prepared as described above, a bond line having a thickness of ˜1 mil was formed between the 4 mm × 4 mm quartz die and the borosilicate glass substrate. In addition, all samples using the respective formulations were UV cured through the quartz glass die (˜550 mJ / cm 2 UVA dose, Dymax fixed curing unit, 100 W Hg arc, etc.). After the initial UV curing reaction, half of all samples using the two formulations were thermally annealed for 10 minutes at a temperature of 70 ° C., and the other half was heated for 1 hour at a temperature of 175 ° C. Cured. Then, the Royce shear test apparatus was used to evaluate the adhesion performance of the samples. The shear test for each sample was performed at room temperature and the results of each test are shown in Table 5. Each data was taken as the average of the values obtained by testing at least four times on average.

Table 5: Shear Test Data

Formulation Shear strength (kg) (curing condition: UV + 70 ° C./10 min) Shear strength (kg) (curing condition: UV + 175 ° C / 1 hour) 30-1 (radial hybrid (2)) 12.3 44.6 30-2 (Epon 828) 22.9 33.7

Formulation 30-2 can be taken as a control adhesive system based on Epon 828, which is essentially a diglycidyl ether of bisphenol A, which is a conventional epoxy resin. From the data shown in Table 5, Formulation 30-1 based on the radial hybrid epoxy resin (2) has a higher shear strength after UV curing and a simple annealing process at 70 ° C. compared to the control Epon 828. It is high. This is because the UV curing reaction rate and the conversion rate of the hybrid epoxy 2 used in the above embodiments are fast. By such a rapid and relatively large-scale UV curing reaction, good adhesiveness and cohesive strength can be obtained, so that the adhesive based on the hybrid resin or the like hybrid resin can be quickly cured. On the other hand, the shear strength data obtained after complete heat curing at a temperature of 175 ° C. for 1 hour shows that formulation 30-2 based on Epon 828 finally shows higher shear strength than formulation 30-1 based on hybrid epoxy based. can confirm. However, it can be seen that Formulation 30-1 also exhibits very high shear strength after a long heat curing cycle, and this level of shear strength is very suitable for various adhesive applications.

Claims (57)

Organic / inorganic hybrid copolymers having an epoxy end and represented by the following structural formula: (In the above structural formula,  n = 1 to 100, q = 1 to 20, the core is an organic unit, block A is an inorganic unit such as a silane unit, a siloxane unit, or a mixture thereof, and block B is an organic unit , R is alkyl, or H, and one or more R groups can be part of a cyclic structure; when q is 1 or 2, block B does not contain ether functional groups in the main chain). The method of claim 1, q = 3-20, The copolymer characterized by the above-mentioned. The method of claim 2, q = 3 to 6, characterized in that the copolymer. The method of claim 1, n = 1 to 5, characterized in that the copolymer. The method of claim 1, Copolymer, characterized in that the core is derived from the group consisting of a hydrocarbon moiety (hydrocarbon moiety) having a plurality of unsaturated substituents. The method of claim 5, The core is tetraallylbisphenol A; 2,5-diallylphenol, allyl ether; Trimethylolpropane triallyl ether; Pentaerythritol tetraallyl ether; Triallyl isocyanurate; Triallyl cyanurate; And copolymers characterized in that derived from the group consisting of these. The method of claim 1, q is 2 and the core is diallylbisphenol A; 1,4-divinyl benzene; Or copolymers derived from 1,3-divinyl benzene. The method of claim 1, Block B is a linear or branched alkyl unit, a linear or branched alkyl unit comprising a hetero atom, a cycloalkyl unit, a cycloalkyl unit comprising a hetero atom, an aromatic unit, a substituted aromatic unit, a heteroaromatic unit, or these Copolymer comprising a mixture of. The method of claim 8, Block B is 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,3-butadiene; 1,5-hexadiene; Copolymers derived from the group consisting of ethylene and mixtures thereof. The method of claim 1, The block A is 1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; Bis (dimethylsilyl) ethane (1,1,4,4-tetramethyldisylethylene); 1,4-bis (dimethylsilyl) benzene; 1,3-bis (dimethylsilyl) benzene; A copolymer characterized in that it is derived from the group consisting of 1,2-bis (dimethylsilyl) benzene, and mixtures thereof. The method of claim 2, Block B is diallyl ether, bisphenol A diallyl ether, 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,3-butadiene; 1,5-hexadiene; Copolymers derived from the group consisting of ethylene and mixtures thereof. The method of claim 1, Copolymer, characterized in that the epoxy end group is derived through hydrosilation reaction (hydrosilation) of the unsaturated epoxy compound. The method of claim 12, And the epoxy end group is derived from the group consisting of vinylcyclohexene oxide, allyl glycidyl ether, 3,4-epoxy butene, limonene mono-oxide, and mixtures thereof. A composition comprising the copolymer of claim 1. The method of claim 14, Wherein the composition is photocurable, electron beam curable, or thermally curable. The method of claim 14, Wherein said composition comprises an adhesive, a sealant, a coating, or a sealant or encapsulant for an organic light emitting diode. A radial organic / inorganic hybrid copolymer having a SiH terminus represented by the following structural formula: (In the above structural formula,  n = 0-100, q = 3-20, the core is defined as an organic unit, the block A is an inorganic unit such as a silane unit, a siloxane unit, or a mixture thereof, and the last unit of the copolymer And the block B is an organic unit. The method of claim 17, q = 3 to 6, characterized in that the copolymer. The method of claim 17, n = 0 to 5, characterized in that the copolymer. The method of claim 17, Copolymer, characterized in that the core is derived from the group consisting of an aromatic hydrocarbon moiety having a plurality of unsaturated substituents. The method of claim 17, The core is tetraallylbisphenol A; 2,5-diallylphenol, allyl ether; Trimethylolpropane triallyl ether; Pentaerythritol tetraallyl ether; Triallyl isocyanurate; Triallyl cyanurate; And copolymers characterized in that derived from the group consisting of these. The method of claim 17, Block B is a linear or branched alkyl unit, a linear or branched alkyl unit comprising a hetero atom, a cycloalkyl unit, a cycloalkyl unit comprising a hetero atom, an aromatic unit, a substituted aromatic unit, a heteroaromatic unit, or these Copolymer comprising a mixture of. The method of claim 22, Block B is 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,3-butadiene; 1,5-hexadiene; Diallyl ethers; Bisphenol A diallyl ether; Copolymers derived from the group consisting of ethylene and mixtures thereof. The method of claim 17, The block A is 1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; Bis (dimethylsilyl) ethane (1,1,4,4-tetramethyldisylethylene); 1,4-bis (dimethylsilyl) benzene; 1,3-bis (dimethylsilyl) benzene; A copolymer characterized in that it is derived from the group consisting of 1,2-bis (dimethylsilyl) benzene, and mixtures thereof. A composition comprising the copolymer of claim 17. The method of claim 25, Wherein the composition is photocurable, electron beam curable, or thermally curable. The method of claim 25, Wherein said composition comprises an adhesive, a sealant, a coating, or a sealant or encapsulant for an organic light emitting diode. Hybrid copolymers having olefinic ends and represented by the following structural formulas: (In the above structural formula,  n = 1-100, q = 3-20, the core is an organic unit, the block B is an organic unit, the block A is an inorganic unit such as a silane unit, a siloxane unit, or a mixture thereof, and R Is defined as alkyl or H, wherein one or more R groups can be part of a cyclic structure). The method of claim 28, q = 3 to 6, characterized in that the copolymer. The method of claim 28, n = 1 to 5, characterized in that the copolymer. The method of claim 28, Copolymer, characterized in that the core is derived from the group consisting of an aromatic hydrocarbon moiety having a plurality of unsaturated substituents. The method of claim 31, wherein The core is tetraallylbisphenol A; 2,5-diallylphenol, allyl ether; Trimethylolpropane triallyl ether; Pentaerythritol tetraallyl ether; Triallyl isocyanurate; Triallyl cyanurate; And copolymers characterized in that derived from the group consisting of these. The method of claim 28, Block B is a linear or branched alkyl unit, a linear or branched alkyl unit comprising a hetero atom, a cycloalkyl unit, a cycloalkyl unit comprising a hetero atom, an aromatic unit, a substituted aromatic unit, a heteroaromatic unit, or these Copolymer comprising a mixture of. The method of claim 33, wherein Block B is 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,3-butadiene; 1,5-hexadiene; Diallyl ethers; Bisphenol A diallyl ether; Copolymers derived from the group consisting of ethylene and mixtures thereof. The method of claim 30, The block A is 1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; Bis (dimethylsilyl) ethane (1,1,4,4-tetramethyldisylethylene); 1,4-bis (dimethylsilyl) benzene; 1,3-bis (dimethylsilyl) benzene; A copolymer characterized in that it is derived from the group consisting of 1,2-bis (dimethylsilyl) benzene, and mixtures thereof. A composition comprising the copolymer of claim 28. The method of claim 36, Wherein the composition is photocurable, electron beam curable, or thermally curable. The method of claim 36, Wherein said composition comprises an adhesive, a sealant, a coating, or a sealant or encapsulant for an organic light emitting diode. Hybrid copolymers having an epoxy end and represented by the following structural formula: (In the above structural formula, n = 1 to 100, q = 1 to 20, the core ₁ is an inorganic unit, the block C is an organic unit, the block D is an inorganic unit such as a silane unit, a siloxane unit, or a mixture thereof, R is defined as alkyl or H, wherein one or more R groups can be part of a cyclic structure; when q is 1 or 2, said block C does not contain ether functional groups in the main chain). The method of claim 39, q = 3-20, The copolymer characterized by the above-mentioned. The method of claim 40, q = 3 to 6, characterized in that the copolymer. The method of claim 39, n = 1 to 5, characterized in that the copolymer. The method of claim 39, The core ₁ is 1,3,5,7-tetramethylcyclotetrasiloxane (D ′ ₄ ); Tetrakis (dimethylsiloxy) silane; octakis (dimethylsiloxy) octaprismosil sequioxane [octakis (dimethylsiloxy) octaprismosilsequioxane]; And copolymers characterized in that derived from the group consisting of these. The method of claim 41, wherein Block C is 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,3-butadiene; 1,5-hexadiene; Diallyl ethers; Bisphenol A diallyl ether; Copolymers derived from the group consisting of ethylene and mixtures thereof. The method of claim 39, The block D is 1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; Bis (dimethylsilyl) ethane (1,1,4,4-tetramethyldisylethylene); 1,4-bis (dimethylsilyl) benzene; 1,3-bis (dimethylsilyl) benzene; A copolymer characterized in that it is derived from the group consisting of 1,2-bis (dimethylsilyl) benzene, and mixtures thereof. A composition comprising the copolymer of claim 39. 47. The method of claim 46 wherein Wherein the composition is photocurable, electron beam curable, or thermally curable. 47. The method of claim 46 wherein Wherein said composition comprises an adhesive, a sealant, a coating, or a sealant or encapsulant for an organic light emitting diode. Hybrid copolymers having a structure selected from the group comprising the following structural formulas: , And (In each structural formula above,  When the copolymer is a copolymer having an olefin terminal, n = 0 to 100; when the copolymer is a copolymer having an SiH terminal, n = 1 to 100; The core ₁ is an inorganic unit, the block C is an organic unit, the block D is an inorganic unit such as a silane unit, a siloxane unit, or a mixture thereof, and R is defined as alkyl or H, wherein one or more R group may be part of an annular structure). The method of claim 49, q = 3 to 6, characterized in that the copolymer. The method of claim 49, The copolymer is n = 1 to 5 when the copolymer is a copolymer having an SiH terminal, and n = 0 to 5 when the copolymer is a copolymer having an olefin terminal. The method of claim 49, The core ₁ is 1,3,5,7-tetramethylcyclotetrasiloxane (D ′ ₄ ); Tetrakis (dimethylsiloxy) silane; Octakis (dimethylsiloxy) octaprismosil sequioxane; And copolymers characterized in that derived from the group consisting of these. The method of claim 49, Block C is 1,3-bis (alphamethyl) styrene; Dicyclopentadiene; 1,4-divinyl benzene; 1,3-divinyl benzene; 5-vinyl-2-norbornene; 2,5-norbornadiene; Vinylcyclohexene; 1,3-butadiene; 1,5-hexadiene; Diallyl ethers; Bisphenol A diallyl ether; Copolymers derived from the group consisting of ethylene and mixtures thereof. The method of claim 51, The block D is 1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; Bis (dimethylsilyl) ethane (1,1,4,4-tetramethyldisylethylene); 1,4-bis (dimethylsilyl) benzene; 1,3-bis (dimethylsilyl) benzene; A copolymer characterized in that it is derived from the group consisting of 1,2-bis (dimethylsilyl) benzene, and mixtures thereof. A composition comprising the copolymer of claim 49. The method of claim 55, Wherein the composition is photocurable, electron beam curable, or thermally curable. The method of claim 55, Wherein said composition comprises an adhesive, a sealant, a coating, or a sealant or encapsulant for an organic light emitting diode.